CN101647436A - Trifloxystrobin microemulsion and manufacturing method thereof - Google Patents
Trifloxystrobin microemulsion and manufacturing method thereof Download PDFInfo
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- CN101647436A CN101647436A CN200910159606A CN200910159606A CN101647436A CN 101647436 A CN101647436 A CN 101647436A CN 200910159606 A CN200910159606 A CN 200910159606A CN 200910159606 A CN200910159606 A CN 200910159606A CN 101647436 A CN101647436 A CN 101647436A
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- oxime bacterium
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- bacterium ester
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Abstract
The invention discloses a trifloxystrobin microemulsion and a manufacturing method thereof. The trifloxystrobin microemulsion is prepared from 5-20 percent of trifloxystrobin, 0.5-15 percent of solvent, 0.5-10 percent of cosolvent, 1-5 percent of penetrant, 8-20 percent of surface active agent and the balance of water. The trifloxystrobin microemulsion has simple and easy production process, highproduction efficiency and better drug effect, improves the medicament use ratio, overcomes some defects of the prior dosage form, and avoids the problems of dust pollution, high energy consumption, low production efficiency and environmental pollution caused by using a great amount of the organic solvent.
Description
Technical field
The present invention relates to a kind of oxime bacterium ester microemulsion and manufacture method thereof, belong to the pesticidal preparations processing technique field.
Background technology
Oxime bacterium ester, chemical name: (2Z)-and 2-methoxyimino-2-[2-[[1-[3-(trifluoromethyl) phenyl] ethyleneimino] the oxygen methyl] phenyl] methyl acetate, English common name Trifloxystrobin, molecular formula: C
20H
19F
3N
2O
4, molecular weight: 408.3, CAS number: 141517-21-7, white solid, 72.9 ℃ of fusing points, boiling point: 312 ℃, be soluble in multiple organic solvent.Oxime bacterium ester is the new fluorine-containing methoxy acrylate bactericide of a class that utilizes natural products Strobilurins successfully to develop as lead compound, characteristics such as having efficient, wide spectrum, protection, treat, root out, infiltration, systemic activity, resistance of rainwater washing against, lasting period are long.To 1, the bacterial strain of 4-demethylation enzyme inhibitor, benzamides, dicarboxylic dihydrazides amine and benzimidazole generation resistance is effective, does not have cross resistance with at present existing bactericide.Nearly all Mycophytes (Ascomycetes, Basidiomycetes, Oomycete and Fungi Imperfecti) disease such as powdery mildew, rust, Ying's rot, net blotch, downy mildew, rice blast etc. all there is good activity.Except that powdery mildew, leaf spot are had the special efficacy, rust, downy mildew, damping off, apple apple scab all there is good activity, to crop safety.Capable of being fast degraded in soil, water because of it, so environmentally safe.
Oxime bacterium ester prior dosage form has missible oil, wetting powder, suspending agent, water dispersible granules, dry suspending agent etc., but does not see the report of microemulsion.Prior dosage form exists some significantly not enough, as there being a large amount of organic solvents in the cream preparation, is a kind of potential pressure to environment; Wetting powder is easy to generate dust pollution in production, transportation, use, the process power consumption, and the medicament particle diameter is bigger, influences the absorption conduction of medicament; It is low that water dispersible granules, dry suspending agent production process are easy to generate dust pollution, power consumption, production efficiency; The power consumption of suspending agent production process, efficient is lower, and the medicament particle diameter is big, is unfavorable for the absorption and the conduction of medicament, and under the natural gravity effect, soup precipitates the knot end easily.Microemulsion is main dispersion medium with water, and production technology is simple, has overcome some shortcomings of existing formulation, for being worth the novel form of development.This formulation is based on proposing the microemulsion theory by Schulman and Hoar in nineteen forty-three, and its theory and application development are very rapid.Microemulsion is normally mixed with surfactant and alcohols by water, oil, can spontaneously form transparent and translucent dispersion, also can utilize the polarity non-ionic surface active agent to obtain under the condition that does not add alcohol.Microemulsion is compared with common emulsion, and have special nature: interfacial tension is little, is generally 10
--5N/m-10
--9N/m; The micella particle is very little, and diameter is about 10nm-100nm; Thermodynamics is more stable, can spontaneously form, and does not need the external world that energy is provided, and separates through high speed centrifugation lamination does not take place; Appearance transparent or intimate transparent.
Summary of the invention
The purpose of this invention is to provide a kind of oxime bacterium ester microemulsion and manufacture method thereof, overcome some shortcomings that existing formulation exists, reduce the pressure of organic solvent, improve the safety of production, packing, transportation, use environment.
The oxime bacterium ester microemulsion that the present invention relates to is characterized by and contains oxime bacterium ester 5%-20%, solvent 0.5-15%, cosolvent 0.5-10%, bleeding agent 1%-5%, surfactant 8%-20%, water and mend to 100%.
The solvent that the present invention relates to is characterized by in turpentine oil, the gaultherolin at least a.Turpentine oil includes gum turpentine, steam-distilled turpentine.During use, according to the difference of oxime bacterium ester content, two kinds of solvents can be singly with or arbitrary proportion be used in combination.
The cosolvent that the present invention relates to is characterized by in alcohols, the ketone at least a, wherein, alcohols comprises ethanol, propyl alcohol, isopropyl alcohol, n-butanol, isobutanol, amylalcohol, isoamyl alcohol, hexanol, enanthol, octanol, nonyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, cyclopentanol, cyclohexanol, phenmethylol, abienol, ethylene glycol, propane diols, 1,2-propane diols, 1, ammediol, glycerine etc.; Ketone comprises acetone, butanone, acetophenone, propiophenone, N-Methyl pyrrolidone, N-ethyl pyrrolidone etc.
The bleeding agent that the present invention relates to is characterized by and comprises penetrant t, JFC, organic silicon surfactant, water-soluble azone.Penetrant t has another name called the succinate sodium sulfonate, and chemical name is the dioctyl maleate sodium sulfonate; Water-soluble azone, chemical name are 1-positive dodecyl aza cyclohepta-2-ketone.
The surfactant that the present invention relates to can be selected from least a in polyethers, ester class, phosphoric acid ester, sulfonate, the Sulfates.
Described polyethers comprises alkylphenol polyoxyethylene class (as: NP/OP-4,6,7,9,10,12,15,20,30,40), benzylphenol polyethenoxy ether class (as: No. 300, farming breast, No. 900, farming breast, No. 31, peaceful breast, No. 36, peaceful breast, the newborn BP of farming), phenethyl phenol polyethenoxy ethers (as: No. 601, farming breast, No. 602, farming breast, No. 603, farming breast, No. 604, farming breast), phenethyl fluosite polyethenoxy ether class (as: No. 401, farming breast, No. 402, farming breast, No. 403, farming breast, No. 404, farming breast), the alkyl phenol formaldehyde resin polyoxyethylene ether class (as: comprises No. 701, farming breast, No. 702, farming breast), fatty alcohol polyethenoxy ether class (as: AEO-3,5,7,9,10,15,20, paregal O, O-20, A-20, SA-20, JFC), phenethyl phenol polyethenoxy polyoxypropylene ethers (as: No. 1600, farming breast, No. 1601, farming breast, No. 1602, farming breast), triphen ethyl phenol polyoxyethylene poly-oxygen propylene aether class (as: No. 33, farming breast, No. 34, farming breast), sorbitan fatty acid ester polyethenoxy ether class (as: polysorbas20, polysorbate40, polysorbate60, Tween 80, polysorbate85), castor oil polyoxyethylene ether class (as: EL-20,40,60,80,90,125; BY-110,120,125,130,140,155).
Described ester class comprises sorbitan fatty acid ester class (as: span 20, span 40, sorbester p18, sorbester p17, sorbester p37), polyoxyethylene carboxylate class, general molecular formula RCOO-(CH
2CH
2O)
nH, cithrol class (as: diethylene glycol monostearate, diethylene glycol bis-stearate, PEG400 monostearate, the two stearates of PEG400, the two stearates of Macrogol 6000).
Described phosphoric acid ester comprises alkyl phenol polyoxyethylene nonylphenol ether phosphoric acid fat and salt, fatty alcohol-polyoxyethylene ether phosphoric acid fat and salt, octyl phosphate and salt thereof, octanol polyoxyethylene ether phosphate and salt thereof etc.
Described Sulfonates comprises neopelex, calcium dodecyl benzene sulfonate, magnesium dodecyl benzene sulfonate etc.
Described Sulfates comprises lauryl sodium sulfate, Stepanol MG etc.
The water that the present invention relates to can be for the water of determining total hardness of water less than 342mg/L (in CaCO3), as running water, deionized water etc.
It is thinner than other formulation that the oxime bacterium ester microemulsion that the present invention relates to is converted water dilution back soup particle, helps the absorption conduction of medicament, improves the active component availability, promotes drug effect.
The process for producing of the oxime bacterium ester microemulsion that the present invention relates to, its preparation process is as follows:
Preparation technology one: at ambient temperature, earlier oxime bacterium ester, solvent, cosolvent, bleeding agent, surfactant are added in the reactor by the requirement of raw material mass percent, under 100-5000 rev/min rotating speed, stir, stirred 15-45 minute, and formed oil phase, keep rotating speed, slowly add entry again, stirred 10-30 minute, and made it to become the liquid of homogeneous, promptly get oxime bacterium ester microemulsion.
Preparation technology two: at ambient temperature, earlier oxime bacterium ester, solvent, cosolvent are added in the reactor by the requirement of raw material mass percent, stir under 100-5000 rev/min rotating speed, stirred 15-45 minute, make it to become the liquid of homogeneous, form oil phase; In another reactor, add bleeding agent, surfactant, water, under 100-5000 rev/min rotating speed, stir, stirred 10-30 minute, make it to become the liquid of homogeneous, form water, keep rotating speed, oil phase is slowly added aqueous phase, stirred 10-30 minute, and made it to become the liquid of homogeneous, promptly get oxime bacterium ester microemulsion.
The oxime bacterium ester microemulsion that the present invention relates to is compared with prior dosage form has outstanding characteristics and significantly progressive: oxime bacterium ester microemulsion adopts water as main medium, not only reduced the use of organic solvent, reduced preparation toxicity, avoided of the pollution of " triphen " class organic solvent to environment, and cheap (comparing production/cost of material with other formulation such as missible oil greatly reduces), make production, packing, transportation, the use of product safer; It is thinner than missible oil that oxime bacterium ester microemulsion is converted water dilution back soup particle, helps crop and absorb, and improved the availability of medicament; The processing technology of oxime bacterium ester microemulsion is simple, and the production efficiency height has been avoided problems such as dust pollution, high energy consumption, poor efficiency, organic solvent pollution.
Embodiment
In order to make the object of the invention and technical scheme clearer, give detailed explanation by the following specific embodiments, but be not limited to these concrete examples.
Example of formulations
Embodiment 1 adopts preparation technology one to produce, in reactor, add (95%) 53 kilogram of the former medicine of oxime bacterium ester, 10 kilograms of water-soluble azones, 50 kilograms in turpentine oil, 50 kilograms of ethanol, 25 kilograms of No. 1600, farming breasts, BY-12525 kilogram, 30 kilograms of lauryl sodium sulfate, stir, add 757 kilograms of entry, stir, promptly get 5% oxime bacterium ester microemulsion.
Embodiment 2 adopts preparation technology one to produce, and adds (95%) 131.6 kilogram of the former medicine of oxime bacterium ester, 3 kilograms of penetrant ts in reactor, 50 kilograms in turpentine oil, 50 kilograms of gaultherolins, 50 kilograms of isobutanols, 30 kilograms of N-Methyl pyrrolidone, 40 kilograms of No. 1601, farming breasts, 30 kilograms of No. 701, farming breasts, 30 kilograms in polyoxyethylene nonylphenol ether phosphoric acid fat, 50 kilograms of calcium dodecyl benzene sulfonates stir, and add 535.4 kilograms of entry, stir, promptly get 12.5% oxime bacterium ester microemulsion.
Embodiment 3 adopts preparation technology one to produce, and adds (95%) 210.6 kilogram of the former medicine of oxime bacterium ester, 100 kilograms in turpentine oil in reactor, 50 kilograms of gaultherolins, 20 kilograms of butanone, 80 kilograms of nonyl alcohols, 20 kilograms of penetrant ts, 15 kilograms of organic silicon surfactants, 50 kilograms of NP-7,40 kilograms of the two stearates of PEG400,50 kilograms of Arlacel-60s, 60 kilograms of neopelexes stir, and add 304.4 kilograms of entry, stir, promptly get 20% oxime bacterium ester microemulsion.
Embodiment 1～embodiment 3 also can produce according to preparation technology two.
Oxime bacterium ester microemulsion formulation stability and average particle size are measured.
With reference to GB/T 19136-2003 method, measure oxime bacterium ester microemulsion storage-stable.Medicament is sealed in the ampoule bottle, places 54 ± 2 ℃ of incubators respectively, in 0 ± 2 ℃ ,-18 ℃ the refrigerator, preserves continuously 14 days, observes the preparation appearance stability, analyzes oxime bacterium ester content.
Table one different content oxime bacterium ester microemulsion storage-stable result of the test (14 days)
| Title | 5% oxime bacterium ester microemulsion (embodiment 1) | 12.5% oxime bacterium ester microemulsion (embodiment 2) | 20% oxime bacterium ester microemulsion (embodiment 3) |
| Heat storage sample content | ??5.04 | ??12.52 | ??20.13 |
| Cold storage sample content | ??5.15 | ??12.71 | ??20.55 |
| Resolution ratio (%) | ??2.14 | ??1.50 | ??2.04 |
From table one data as can be seen, oxime bacterium ester storage-stable is good in the oxime bacterium ester microemulsion of different content, and resolution ratio complies with the national standard requirements all less than 5%.
Table two different content oxime bacterium ester microemulsion storage-stable test appearance change (14 days)
| Temperature | 5% oxime bacterium ester microemulsion (embodiment 1) | 12.5% oxime bacterium ester microemulsion (embodiment 2) | 20% oxime bacterium ester microemulsion (embodiment 3) |
| ??54±2℃ | Homogeneous, transparent clear | Homogeneous, transparent clear | Homogeneous, transparent clear |
| ??0±2℃ | Homogeneous, transparent clear | Homogeneous, transparent clear | Homogeneous, transparent clear |
| ??-18℃ | Homogeneous, transparent clear | Homogeneous, transparent clear | Translucent, room temperature can be recovered homogeneous, transparent clear voluntarily |
As can be seen from Table II, through storage test, oxime bacterium ester microemulsion formulation outward appearance is good, and the preparation outward appearance also can be recovered normally to comply with the national standard requirements voluntarily under the extreme low temperature condition.
Particle size when adopting the laser particle size distribution instrument to measure different dosage form such as oxime bacterium ester microemulsion to convert 200 times of water dilutions.
Average grain diameter (μ m) size measurement result when different dosage forms such as table trioxime bacterium ester microemulsion are converted 200 times of water dilutions
| Preparation | 5% oxime bacterium ester microemulsion (embodiment 1) | (embodiment 2 for 12.5% oxime bacterium ester microemulsion | 20% oxime bacterium ester microemulsion (embodiment 3) | 20% oxime bacterium emulsifiable concentrate (dimethylbenzene is main solvent) | 20% oxime bacterium ester wetting powder | 20% oxime bacterium ester suspending agent | 20% trifloxystrobin water dispersible granule |
| Average grain diameter size (μ m) | ? ??0.015 | ? ??0.021 | ? ??0.027 | ? ??27 | ? ??50 | ? ??45 | ? ??60 |
From table three data as can be seen, the oxime bacterium ester microemulsion average grain diameter of converting water diluent is far smaller than the average grain diameter of missible oil, wetting powder, suspending agent, water dispersible granules.
Test of pesticide effectiveness embodiment
Embodiment 4 adopts pot-culture method to measure the therapeutic action of different dosage forms such as 20% oxime bacterium ester microemulsion (embodiment 3), missible oil, wetting powder, suspending agent, water dispersible granules to powdery mildew of cucumber indoor, and result of the test is as follows:
Table four adopts pot-culture method to measure the indoor therapeutic action result that different dosage form such as 20% oxime bacterium ester microemulsion is prevented and treated the powdery mildew of cucumber bacterium
From the table data as can be seen, 20% oxime bacterium ester microemulsion slightly is better than 20% oxime bacterium emulsifiable concentrate to the result of treatment of powdery mildew of cucumber, significantly better than other formulations such as 20% oxime bacterium ester wetting powder, suspending agent, water dispersible granules.
Claims (6)
1, a kind of oxime bacterium ester microemulsion is characterized by and contains oxime bacterium ester 5%-20%, solvent 0.5-15%, cosolvent 0.5-10%, bleeding agent 1%-5%, surfactant 8%-20%, water and mend to 100%.
2, solvent according to claim 1 is characterized by in turpentine oil, the gaultherolin at least a.
3, cosolvent according to claim 1, it is characterized by in alcohols, the ketone at least a, wherein, alcohols comprises ethanol, propyl alcohol, isopropyl alcohol, n-butanol, isobutanol, amylalcohol, isoamyl alcohol, hexanol, enanthol, octanol, nonyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, cyclopentanol, cyclohexanol, phenmethylol, abienol, ethylene glycol, propane diols, 1,2-propane diols, 1, ammediol, glycerine; Ketone comprises acetone, butanone, acetophenone, propiophenone, N-Methyl pyrrolidone, N-ethyl pyrrolidone.
4, bleeding agent according to claim 1 is characterized by in penetrant t, JFC, organic silicon surfactant, the water-soluble azone at least a.
5, surfactant according to claim 1, it is characterized by that to be selected from polyethers, ester class, phosphoric acid ester, sulfonate, Sulfates at least a, wherein, polyethers comprises alkylphenol polyoxyethylene, benzylphenol APEO, phenethyl phenol polyethenoxy ether, phenethyl fluosite APEO, alkyl phenol formaldehyde resin polyoxyethylene ether, fatty alcohol-polyoxyethylene ether, phenethyl phenol polyethenoxy polyethenoxy ether, triphen ethyl phenol polyoxyethylene poly-oxygen propylene aether, sorbitan fatty acid ester APEO, castor oil polyoxyethylene ether; The ester class comprises sorbitan fatty acid ester, polyoxyethylene carboxylate, cithrol; Phosphoric acid ester comprises alkyl phenol polyoxyethylene nonylphenol ether phosphoric acid fat and salt, fatty alcohol-polyoxyethylene ether phosphoric acid fat and salt, octyl phosphate and salt thereof, octanol polyoxyethylene ether phosphate and salt thereof; Sulfonates includes neopelex, calcium dodecyl benzene sulfonate, magnesium dodecyl benzene sulfonate; Sulfates includes lauryl sodium sulfate, Stepanol MG.
6, the process for producing of the described oxime bacterium of claim 1 ester microemulsion, its feature is as follows:
Preparation technology one: at ambient temperature, earlier oxime bacterium ester, solvent, cosolvent, bleeding agent, surfactant are added in the reactor by the requirement of raw material mass percent, under 100-5000 rev/min rotating speed, stir, stirred 15-45 minute, and formed oil phase, keep rotating speed, slowly add entry again, stirred 10-30 minute, and made it to become the liquid of homogeneous, promptly get oxime bacterium ester microemulsion.
Preparation technology two: at ambient temperature, earlier oxime bacterium ester, solvent, cosolvent are added in the reactor by the requirement of raw material mass percent, stir under 100-5000 rev/min rotating speed, stirred 15-45 minute, make it to become the liquid of homogeneous, form oil phase; In another reactor, add bleeding agent, surfactant, water, under 100-5000 rev/min rotating speed, stir, stirred 10-30 minute, make it to become the liquid of homogeneous, form water, keep rotating speed, oil phase is slowly added aqueous phase, stirred 10-30 minute, and made it to become the liquid of homogeneous, promptly get oxime bacterium ester microemulsion.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102239879A (en) * | 2011-04-02 | 2011-11-16 | 陕西汤普森生物科技有限公司 | Bactericidal composition containing trifloxystrobin |
| CN102450252A (en) * | 2010-10-20 | 2012-05-16 | 周端午 | Green, long-lasting antibacterial, mildew-resistant and insecticidal water-based micro-emulsifier |
| CN105076132A (en) * | 2015-06-11 | 2015-11-25 | 中国农业大学 | Oil-based type pesticide synergistic auxiliary and preparation method therefor |
| US10172359B2 (en) * | 2017-05-17 | 2019-01-08 | Sergeant's Pet Care Products, Inc. | Solvent system for use with spot-on pesticide compositions |
-
2009
- 2009-07-21 CN CN200910159606A patent/CN101647436A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102450252A (en) * | 2010-10-20 | 2012-05-16 | 周端午 | Green, long-lasting antibacterial, mildew-resistant and insecticidal water-based micro-emulsifier |
| CN102239879A (en) * | 2011-04-02 | 2011-11-16 | 陕西汤普森生物科技有限公司 | Bactericidal composition containing trifloxystrobin |
| CN102239879B (en) * | 2011-04-02 | 2013-11-06 | 陕西汤普森生物科技有限公司 | Bactericidal composition containing trifloxystrobin |
| CN105076132A (en) * | 2015-06-11 | 2015-11-25 | 中国农业大学 | Oil-based type pesticide synergistic auxiliary and preparation method therefor |
| US10172359B2 (en) * | 2017-05-17 | 2019-01-08 | Sergeant's Pet Care Products, Inc. | Solvent system for use with spot-on pesticide compositions |
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Application publication date: 20100217 |